Conventional benzoxazine is difficult for molding and manufacturing parts with complex structures, shaped thin walls, etc. In this work, we presented a new method of synthesizing vat photopolymerization 3D printable benzoxazine inks were proposed to produce high precision constructions with low shrinkage. A creative benzoxazine monomer with excellent printability was synthesized by 2,2′-bis(trif luoromethyl)-4,4′-diaminobiphenyl (TFDB) and Bisphenol AF grafting with isocyanoethyl methacrylate (IEM). Specially, the solvent-free benzoxazine inks have ultra-low shrinkage, line shrinkage up to 1.8%. Minimum printable feature size of 300 µm. This study has solved the problem of benzoxazine being too brittle to be machining. It can be used in aerospace and copper laminate applications.